Process for converting hydrocarbons



Sept. 4, B945.

'F. E. FREY PROCESS FOR CONVERTING HYDROCARBONS Filed July l1, 1942 2 Sheets-Sheet 1 Y E R F E h PROCESS FOR COHVERTING HYDROCARBON Filed July 11, 1942 2 vSheets-Sheet 2 N .um

HOLVNOLLDVtH INVENTOR F EDERICK E FREY R EYS Patented Sept. 4, 1945 unan STATES vPA'rlt-N'i oFFlcE.

2,384,294: PROCESS FOR CONVERTING HYDRO- CARBONS Frederick E. Frey, Bartlesville, Okla., assignor to Phillips Petroleum Company, a corporation oi' Delaware Application July 1l, 1942, Serial No. 450,588

(Cl. 26o-671) 13 Claims.

This invention relates to the conversion of hydrocarbons. More particularly it relates to the use of catalysts, modied by the addition of suitable tempering agents, for eieoting catalytic alkylation of alkylatable hydrocarbons, especially isoparatlinic and aromatic hydrocarbons.

In a typical method of conducting an alkylation reaction, an alkylatable hydrocarbon is agitated with substantially anhydrous hydrouorlc acid to l produce a liquid mixture or emulsion which is maintained at a reaction temperature suitable for alkylation, and an alkylating reactant is introduced in such a way as' to maintain only a very low concentration of alkylating reactant in the mixture. After asuitable reaction time the hydrocarbon layer may be decanted, and the juncture product or alkylate may be separated from the other hydrocarbons, as by fractional distillation. This reaction can be effected not only at temperatures requiring some degree of refrigeration. that is, below room temperature, as

y is the commercial practice when sulfuric acid is used as an allylating catalyst, but also at temperatures equal to and above ordinary temperatures, whereby the need for refrigeration is avoided. Hydrogen fluoride lacks the oxidizing tendency which sulfuric acid possesses and which leads to the formation of sulfur dioxide and sludge compounds in serious degree when the latter catalyst is used for alkylation at elevated temperatures. The alkylation reaction is exceedingly rapid at the higher temperatures; for example, it can be virtually completed in less than three minutes at 125 F. when using butylenes and isobutane as reactants with hydrogen iiuoride as cation, Serial N. 429,962, led February "I, 1942,

olens are absorbed from a hydrocarbon streamv by liquid concentrated hydroiiuoric acid, and the resulting mixture is used to alkylate a suitable alkylatable paraiiln. Because ioi the tendency of olens to polymerize in concentrated hydrouoric acid, the temperature of the acid-olefin mixture must be relatively low, preferably below room temperature, and/or the period oi time elapsing between the absorption step and the alkylation step must be very short, and/or the hydrofiuoric acld-to-oleiin ratio must be relatively high, for example, above 10: 1.

lAn object oi myinventi'on is to increase the yield of primary products in a hydroiiuoric acid alkylation process. Another object is to low-boiling hydrocarbons in hydroiiuoric .acid

' alkylation products.

the catalyst. At such an elevated reaction tem- A further object is to reduce or eliminate the need for refrigeration in producing a product of given characteristics and quality,

A further object is to increase the stability of oleflns in concentrated hydrofluoric acid, particularly against polymerization.

Another object is to decrease the rate of formation of acid-soluble materials, thereby reducing the load on acid-rerun equipment.

Still other objects and advantages of this in-l vention will be apparent from the following description. the accompanying drawings, and/or the appended claims.

I have found that, in an alkylation process catalyzed by hydrofiuoric acid, certain agents may be advantageously added to the acid, to the reaction mixture, or to reactantsin limited proportions to temper the activity of the catalyst and to inhibit deleterious side reactions. Further,.I have found that oleiins, when dissolved in hydroiiuoric acid containing such a tempering agent, retain their usefulness as alkylating agents for longer times lthan when a tempering agent is not present.,

Still further, I have found that most off these agents may be advantageously recovered and recycled to the process.

In accordance with my invention! have found that the additive agents exerting this tempering eiiect are polar compounds which are' preferentially soluble in the hydro'fiuorlc acid phase of alkylation reaction mixtures and which have a inhibit the formation oibases, such as quinoline, aniline, naphthylamines.

toluidine, hexamethylene tetramine, pyridine, piperidine, toluvlene diamine, inorganic ammonim compounds such as ammonium iluoride and the like may be used also; (b) hydroxylated organic compounds including aliphatic and aromatic alcohols such as methanol, ethanol, alcohol amines such as ethanolamine, phenol, catechol and other polyhydric phenols. and organic acids such as acetic, benzoic, tartaric, etc. Secondary or tertiary alcohols, while also operative, are not as desirable because of their tendency to form olens by dehydration, however.'

It will thus be seen that the compounds which may be utilized as tempering agents are those which are relatively basic to hydrofluoric acid and 'are selected froml those which contain basic nitrogen atoms or hydroxyl groups.

'I'he action of the tempering4 agents is not completely understood.l However, it is believed that ingeneral an additive agent, such as one of those mentioned above, lowers the surface tensions and interfacial tension in the vreaction mixtures, and to some extent forms a loose chemical compound or molecular complex with one or more components of the reaction mixture, usually with hydrofluoric acid. A tempering agent, by lowering the interfacial tension between the acid and hydrocarbon phases in the reaction mixture, greatly ascesa:

acid alkylation process, and Figure 2 is a schematiciiow-diagram of an arrangement for practicing this invention in a modined process wherein oleiins are rst absorbed in concentrated hydrouoric acid containing an addition agent and the resulting mixture is used to alwlate a suitable alkylatable hydrocarbon. l

` In Figure l a suitable addition or tempering agent, for example quinoline, aniline, or pyridine,

is admitted to the system through inlet II having valve I2 to mixer Il, wherein it becomes dissolved in liquid concentrated hydrofiuoric acid, which may be admitted through inlet I4 having valve I5. Mixer I3 may be very simple; usually simply imecting the modifying agent into a conduit which carries hydrouoric acid will suffice as a means of mixing. The proportion of tempering agent may be from about 0.01 to about 420 per cent weight of the hydrouoric acid. The optimum concentration depends upon the particular agent used and upon the operating conditions; usually it is in the range from about 0.1 to l0 per cent by weight of the hydrofluoric acid, and it may be readily determined by trial in any particular instance.

' The eliiuent from mixer" I 3 passes through valve I8 and conduit I1 to alkylator 26, wherein it is agitated with a mixture of an alkylatable hydrocarbon. and an alkylating reactant in suitable proportions. This mixture, which may be, for example, an isoparaln, such as isobutane or isopentane, and an olefin, such as propylene or butylene, may be admitted through one or more increases the interfacial surface area which is obtainable by mechanical agltating devices, and

thus facilitates the transfer of the alkylatable hydrocarbon into, and of the primary product out of, the acid phase. Most tempering agents also change the electrical conductivity and/or the dielectric constant of concentrated liquid hydroiluoric acid and therefore presumably a'ect the dissociating and/o ionizing power of the acid. Practically, the effect may be described as a reduction of the action of the acid on freshly formed primary-alkylate and, in some instances, retardation of the rate of reaction of oleilns lin the acid, thereby reducing the extent of side reactions, such as polymerization and cyclization, and decent by weight of the acid, though in many inv stances this range maybe exceeded without passing beyond the scope of this invention; the optimum concentration may be readily determinedA by trial in any particular instance.

Understanding of my invention may be aided by the accompanying drawings in which Figure 1 is a schematic now-diagram of one arrangement for practicing this inventionv in a hydroiluoric inlets, such as inlet 21 controlled by valve 28. lThe alkylating conditions usually may be as follows: temperature, 50 to 200 F.; pressure, sumcient to maintain all components in the liquid phase; contact time or time of residence in al-l kylator l28, l to 30 minutes; vigorous agitation; and, preferably, maintenance of a large excess of the alkylatable hydrocarbon over the alkylating reactant. f

The resulting mixture from alkylator 28 is passed through valve 4l and conduit 46 to separator l1, wherein it is separated into two liquid phases, as by cooling and/or gravitational or centrifugal means.

The lighter or hydrocarbon phase is passed through conduit Il having valve 49 to fractionator 50, wherein it is separated into the following iive fractions: (l) A very minor fraction comprising non-condensable gases, whichmay be withdrawn through outlet 5I having valve I2; 2) a fraction comprising low-boiling alkylatable saturated hycreasing the formation of acid-soluble materials.

drocarbon material, which may be recycled vla 'conduit 58 having valve 51 to alkylator 2i; (3) a fraction comprising excess low-boiling alkylatable hydrocarbon and/or relatively diilicultly alkylatable low-boiling hydrocarbons. which may be removed from the system through outlet Il having.

valvev 58: (4) a fraction comprising -highly branched paraillnic hydrocarbons suitable for use in motor fuel, which may be withdrawn through outlet 60 having valve II; and (5). a relatively small and high-boiling hydrocarbon fraction, which may be withdrawn` through outlet i2 havins valve 8l.

The-heavier or hydrofluoric acid phase from separator 41 may be recycled through valve l and conduit Il tothe acid inlet I4. Preferably, however, at least part of it is passed through valve B9 to acid fractionator 11|, wherein it is separated into two fractions. An overhead fraction comprising substantially .pure anhydrous atively low-boiling .hydrocarbons is passed through valve 'II and conduit l2 to separator 55. A bottom fraction, which comprises mainly acid-soluble hydrocarbons, flucro-organic material, hydrogen fluoride, some incidentally introduced water, and the tempering agent, is passed through valve 14 and conduit I5 toseparatorl.

A stream of water is injected into conduit 'I5 through valve 80 and inlet 8l and is mixed thereinv with the acid sludge or` residue from fractionator l0. The water extracts hydrogen fluoride and ltempering agent from lthe acid sludge. 'I'he carbonaceous materials are substantially insoluble andl separate out in separatorl 1G as an oily layer, which is removed thro-ugh outlet 82 having valve 83.

The aqueous phase is passed from separator. 16 through conduit 85 and valve 86 to a fractionator 81, wherefrom water and hydrogen fluoride are withdrawn overhead through valve 88 and outlet 88, and the recovered tempering agent is withdrawn as a bottom product in condition suitable for recycling to inlet II. as through valve 92 and conduit 83. If desired, part or all of the aqueous overhead fraction from fractionator 8l may be recycled through valve 90 and conduit'8l to conduit 15 for re-use as extracting fluid.

The above-described flow-schemeV is suitable for use with tempering agents or their compounds with hydroluoric acid which are soluble in water or dilute aqueous hydrouoric acid. This is true of many of the preferred agents; however, some may not fall within this category and hence may require different means of recovery for recycling.A Relatively volatile tempering agents that do not form involatile compounds with hydrofluoric acid may be concentrated or recovered by fractional distillation. Relatively high-boiling tempering agents, such as some polyhydric phenols, which are insoluble in water or dilute aqueous hydrogen fluoride may be extracted by some other preferential solvent, such as an alkaline solution. Addition agents which are dissolved in the hydrocarbon phase or products may be recovered similarly by distillation or acid, alkali, or water extraction. steps (not shown in the drawings), as will be =obvious to those skilled in the arts of chemistry and chemical engineering. The most suitable' modification for recovering and recycling theA tempering agents will be apparent to those r skilled in the art from the foregoing discussion, together with a consideration of the properties of the particular agent selectedv for use.

In Figure 2, a suitable addition or tempering agent, for example. quinoline, aniline, or pyridine, is admitted to the system through inlet II and valve I2 to mixer I3, wherein it becomes dissolved in a. liquid concentrated hydrouoric acid phase which may be admitted through inlet I4 having valve I5. The proportion of tempering agent in the hydrofluoric acid may be from about 0.01 to 20 per cent by weight of the acid. The optimum concentration depends upon the which contains oleflns. The olefins are preferably present in proportions of 1 to 50 per cent or more by weight'of the hydrocarbon and are of the type suitable for use as alkylating agents, for example, propylene, butylenes', and/or amylenes. The oleiins are rapidly absorbed in mixer I8 bythe hydroiluoric acid phase, and the resulting mixture is passed through valve 2l and conduit 22 to centrifuge 23 wherein it is separated into an olein-in-acid phase' and a saturatedhydrocarbon phase.

The conditions in. mixer I8 and centrifuge 23 are preferably as follows: temperature, 50 to 200 F.; pressure, sufficient to` maintain all components in the liquid phase; total contact time, 5 seconds to 15 minutes or more; acid-'to-oleiin ratio, 5:1 to 20: 1 by weight. These conditions are considerably less limited than those which I prefer to use when no inhibitor is present in the acid phase. For example, if no inhibitor is used, the preferred conditions are: temperature, 30 to 150 F.; acid-.to-olefln ratio 10:1 to 50:1 by weight or more. operating conditions and advantageously operating under what formerly were'the less favorable conditions, especially oi' the temperature and the acid-oleiin ratio is possible in the process of this invention because the addition agent markedly lowers the tendency of the olenc material dissolved in hydrouoric acid to undergo polymerization and/or other side reactions which adversely affect its utility as an alkylating catalyst.

The olefin-in-acid phasea from centrifuge 23 is passed through valve 2| and conduit 25 to alkylator 26, in which it is agitated under alkylat- -ing conditions with an alkylatable hydrocarbon,

such as isobutane or isopentane, which may be introduced throughl yalve 2l and conduit 28. Preferably, the proportion of' alkylatable hydrocarbon to oleiin is from 2:1 to 15:1 by weight.- The alkylating conditions are preferably as follows: temperature, '15 to 200 F.; pressure, sufcient to maintain all components in the liquid phase; time, 1 .to 30 minutes. Here again the operating conditions may be less favorable or less closely controlled for ,producing a product' of given quality and yield .than when no tempering agentis used; for example, if no addition agent is used, the corresponding preferred temperature range is from about 30 to 150 F. The tempering agent apparently reduces both the extent of side reactions and the tendency of the primary alkylation product to undergo secondary or reconstruction reactions.

The olefin-depleted hydrocarbon phase fron centrifuge 23 passes through valve 28 .and conduit 30 to a distributing means 3lv in washer or absorber 32. The hydrocarbon rises, by virtue of its particular reagent used and upon the operating .relatively low density, countercurrently to downwardly owing hydrouoric acid which may Abe introduced as the concentrated or anhydrous acid near the middle ofthe absorber through inlet 33, valve 34, and distributing means 35. Dissolved organic iiuorides are absorbed from the hydrocarbon phase by the hydrouoric acid, wh'ich, after a short settling period in space 36 at the bottom of the washer is passed through valve 3l and conduit 38 for addition of tempering agent I and for subsequent use as olefin-absorbing liquid in mixer I8. Although as the hydrocarbon rises through the bottom h'alf of absorber 32, the countities of hydroiluoric acid remain dissolved in the Broadening of the range of umiur-products, which is withdrawn above distributing means 35, for example, from a' bubble tray or other collecting device 96. It may be recycled through conduit 95, pump 96, and valve 91 to distributing means Il, or it may be passed by a means not shown on the drawings to an acid-recovery unit, such as fractionator 10. The hydrocarbon phase, after a short settling period in space 42 at the top of washer 32, wherein it is separated from the aqueous phase, is withdrawn through outlet 43 having valve I4; if desired, this material may be passed to a fractionator, not sh'own. to recover isoparatlins for alkyla# tion.

The quantity of water or aqueous dilute hydrofiuoric acid introduced is preferably about onetwentieth to one-tenth of the volume of hydrocarbon treated; a much larger proportion introduces excessive amounts of water into the system, whereas a much smaller proportion does not effect substantially complete recovery of hydrouoric acid from the hydrocarbon. The quantity of concentrated hydroiluoric acid introduced in the central portion of the washer preferably is from onefourth to two times the volume of hydrocarbon treated, andl should be at least five times the volume of aqueous solution introduced at the top of the washer. Smaller amounts do not always completely remove alkyl fluorides from the hydrocarbons or are diluted too much by the aqueous solution from the top of the washer, whereas largerY amounts produce an unnecessarily high ratio of acid to hydrocarbon in alkylator 26.

The reaction product from alkylator 25 passesl through valve 45 and conduit 48 to separator 41, wherein it is sepmated into two liquid phases, as by cooling and/or gravitational or centrifugal means.

Of these phases, the lighter or hydrocarbon phase is passed by way of conduit $8 having valve 49 to fractionation unit 50, in which it is separated by fractional distillation into the following six fractions: (l) a very minorfraction of noncondensable gases which is removed through out let I having valve 52; (2) a relatively minor fraction comprising an azeotropic mixture of hydrogen nuoride and light hydrocarbons, such as, propane, butane, and/or pentane, which' passes through valve 53 and conduit 54 to separator 55;

A (3) a comparatively large fraction comprising unreacted alkylatable hydrocarbons, such as isobutane or isopentane, which is necycled via conduit through outlet having valve 59; (5) a substantial fraction of the desired highly branched par' amnic reaction products boiling within the gasoline range, which is withdrawn through outlet I9 havingvvalve 8|; and (6) :thigh-boiling bottom fraction, comprising heavy polymers and qzher through outlet i2 having valve 93.

'Thev heavier or hydrouoric Yacid ph'ase from A separator 41 may recycled thrduh conduit l means, into two liquid phases.

, lllhaving valve 93.

valve 6B, acid recycle conduit 96 and valve l1 and/or valve 98 to absorber 32 and/or mixer II, respectively. Preferably. however, at least part of it is passed .through valve I9 to acid fractionator 10, in which it is separated by fractional distillation into the following three fractions: (1) a minor low-boiling fraction comprising hydrogen fiuoride and low-boiling hydrocarbons. which is passed through valve 1l and conduit 12 to separator 55; (2) a maior fraction of substantially pure hydrogen fluoride which is passed through valve 1I to acid recycle conduit 68; (3) a kettle fraction comprising water, hydrofluoric acid, tempering agent, and an organic residue, which' is passed through valve 14 and conduit 15 to sepa rator 18.

Separator 55 effects separation of the overhead azeotropes from fractionators 50 and 10 into two liquid phases, as by cooling and gravitational or centrifugal means. The lighter or hydrocarbon phase is withdrawn through' outlet 11 having valve 18; the heavier or hydrofiuoric acid phase is passed through valve 19 to acid recycle conduit 69.

, Into the inhibitor-containing fluid in conduit 15 is injected bysrneans of valve 80 and cond-uit 8l a selective solvent, preferably water or a dilute aqueous solution containing a suitable chemical reagentfto extract the tempering agent. Water or a dilute aqueous solution of hydrofiuoric acid is usually suitable for extracting tempering agents of the basic nitrogen type; alkaline solu'- tions are usually suitable for extracting phenolic or hydroxy organic agents. In separator 1B the resulting mixture from conduit I5 is separated, as by cooling and/ or gravitational or centrifugal The lighter or hydrocarbon phase is withdrawn through outlet The heavier or aqueous phase, containing the tempering agent, may be recycled through valve i and conduit to the top section of absorber I# for use as absorbing iiuid therein; preferably, however, a part of itis `passed through valve 88 to fractionator 91 which separates it into two fractions. The lower-boiling fraction from fractionator 81 comprises mainly water or other solvent and may be withdrawn through outlet'89 having` valve 99; preferably, however, part or all of it is recycled through valve 99 and conduit 9| to conduit 15 for re-use as inhibitor-extracting iiuid.4 The higher-boiling fraction, which comprises substantial proportions of recovered tempering agent or simple chemical derivatives thereof, is recycled through valve 92 and conduit 93 to mixer Il. If desired, the recovered'tempering fagent, may be subjected to known to those skilled in the art,- maybe supl plied\wherever theyare necessary or convenient. 'I'he llarlation conditions hereinbefore described are generally suitable for alkylation of readily alkylatable' hydrocarbons like isoparamns and aromatics of the type fof benzene or toluene with oleilns or with alkyl compounds (alcohols. halides, ethers,-esters, etc.)-'having three or more carbon-atoms in the alkyl group; however, when ethylene or an ethyl compound is used, somowhat more drastic conditions, such as higher temperatures, may be advantageously employed. To illustrate further some of the many aspects of my invention. the following examples are given.

EXAMPLE I rn a process similar to that which is embodied in Figure 2, isobutane is alkylated with mixed butylenes from a C4 refinery gas fraction. Sufv10 ficient quinoline is added to the hydrofluoric acid used to absorb oleflns to give an acid-to-quinoline ratio of 20 to 1 by weight. The operating conditions are about as follows; temperature in the olefin extractor, 105 F.; pressure in olefin extractor, 150 pounds per square inch; time of contact of olefins with hydrouoric acid prior to the alkylation step, 6- minutes; alkylator temperature, 125 F.; alkylator pressure, 125 pounds per square inch; reaction time, 5 minutes; hydrogen iluoride-,to-olefin ratio, 10:1; isobutane-to-olefln ratio 3.5:1. Under these conditions is produced an aviation-gasoline product in high yield and of good quality.

EXAMPLE II To a mixture of 301.2 grams of substantially pure anhydrous hydrofluoric acid, cc. of methanol, and 126 grams of isobutane, agitated at room temperature in a closed container, were slowly added 44.5 grams of butene-l. After a Afew minutes the mixture was withdrawn and all lowed to settle. About 70 cc. of saturated, normally liquid hydrocarbon material having at 68v F. a specific gravity of 0.7277 and a refractive index of 1.4066 was obtained.

EXAMPLES 111, IV, lAND v y Three batch runs, hereinafter referred to as Examples III, IV, ari/d V, were made for allwlating isobutane with butene-l under similar conditions except for the composition of the catalyst. In Example III, the catalyst consisted of anhydrous hydrofluoric acid modified by 5.6

weight per cent of methyl alcohol; in Example IV, it consisted of anhydrous hydrofluoric acid modified by 8.0 Weight per cent of glacial acetic acid; and in Example V, it consisted of unmodifled lanhydrous hydrouoric acid. An 18-liter steel reactor provided with a motor driven 540- R.. P. M. stirrer was used in each run. The vcatalyst and the isobutane were mixed together, and the butene-l was then added at a uniform rate..l After the butene-l had been added, the stirring was continued for a short additional period; the

average contact time of the hydrocarbon reaction mixture with the acid was about the same for al1 three runs. The mixture was allowed to separate into'two layers, and the hydrocarbon layer was removed, acid-freed, debutanized. and 6 0 examined.

Experimental data forthese three examples are given in Table I. It will benoted that the proportion of 'octanes in the total alkylate .was

higher in Example III than in Example V; that the yield of the aviation-gasoline fractions based on total debutanized alkylate was higherr in Examples III and IV than in Example V; that the octane numbers of the aviation-gasoline fractions produced in Examples III and\IV were markedly 7 higher than in Example V; that the lead susceptibility of the aviation-gasoline fraction' from Example III was slightly higher than that from Example V; and that'these favorably different octane-rating effects were obtained in spite of higher cut points used fo'r obtaining the aviationgasoline fractions in Examples III and IV.

Tsar.: I

VHF' alkylation of isobutane with butene-I.

Example III IV V Catalyst modifier Methanol Acetic Acid None Temperature, F.. 100-117 97-113 99-113 Pressure. s. L 78-99 82-100 93-111 Contact t me, mln.:

Olen addition 26 15 17 Further agitation 3 7 6 Avere e 16 14.5 14.5 Isobutane butene ratio wt.) l2. 50 ll. 92 12.85 Total hydrocarbon/H ratio 2 27 w Composition, volume per cent:

Heavier 3. 1

Total 100, 0 Aviation-gasoline fraction:

Cut point, "F l 35e Volume per cent of total alkylate 95.5 97 2 9i. 4 ASTM distillation, F.:

First drop 178 128 192 10 percent evaporated-- 208 184 212 50 per cent evaporated.- 218 221 221 per cent evaporated.. 229 234 229 o End poirgs... 348 384 309 ctane num r 0 cc. TEL 93. 3 92. 5 89.2 l cc. TEL 102. 2 97.8

Because the invention may be practiced otherwise than as specifically described herein, and because many modifications and variations of it will he lobvious-to those skilled in the art, it should not abe restricted except as specified in the appended claims.

1. A process for alkylating relatively lowboiling alkylatable hydrocarbons with relatively low-boiling olefins to produce higher boiling hydrocarbons in the presence of concentrated hydrofluoric acid as a catalyst, which comprises admixing with said hydrouoric acid a minor proportion of a polar organic compound soluble in hydrouoric acid which is one of the group consisting of organic hydroxy compounds and organic oric acid used for contacting said hydrocarbonsv into the alkylation zone as ar portion of the catalyst for the alkylation reaction, removing the `reaction products from the alkylation zone and separating therefrom a light hydrocarbon phase and a heavier hydrofluoric acid phase, recovering from said hydrocarbon phase a fraction essentially comprising hydrocarbon reaction products, fractionating at least a portion of said heavier `between about 0.1 and phase to recover as an overhead fraction substantially pure hydrogen fluoride and a bottom fraction comprising said tempering agent along with hydroiiuoric acid `and undesired impurities,

' atable hydrocarbon with an oleiin to produce higher' boiling hydrocarbons in the presence of a concentrated hydrofluoric acid alkylating catalyst, which comprises adding to liquid concentrated hydroiiuoric acid between about 0.1 to 10 per cent by weight of methyl alcohol as a tempering agent, contacting said tempered liquidv hydrouoric acid with a low-boiling oleiin-containing mixture in a contacting zone to absorb olens in 'said hydrouoric acid. separating a resulting olen-depleted hydrocarbon mixture from a resulting oleiin-rich hydrouorlc acid, passing said olefin-rich acid to an allwlation zone and reacting olens contained therein with a low-boiling alkylatable hydrocarbon in the presence of said hydrouoric acid as an alkylating catalyst, passing eiiluents of said alkylation zone to separating means and separating a hydrocarbon phase from a liquid hydrofiuoricacid phase, recovering hydrocarbon reaction products from said hydrocarbon phase as products of the process, passing a portion of said acid phase to said contacting zone, subjecting a further portion ofV said acid phase to fractional distillation to separate relatively pure hydrofluoric acid as a low-boiling fraction from a high-boiling fraction comprising methyl alcohol and undesired impurities, returning said hydrofiuoric acid to said contacting zone, washing said high-boiling fraction with water to separate-methyl alcohol from said impurities, recovering said methyl alcohol from the resulting `aqueous .solution and returning same to said contacting zone.

3. An, improved process for alkylating hydrocarbons, which comprises reacting under alkylation conditions a low-boiling alkylatable hydrocarbon with an oleiin in the presence ot liquid concentrated hydroiluoric acid associated with per cent by weight of methyl alcohol.

4. In a process for converting relatively lowin the presence of concentrated hydrofluoric acid as a catalyst, which comprises admixing with liquid hydrofluoric acid between about 0.1 to l0 per cent -by weight of a polar organic compound soluble in hydrofluo'ric acid which is one of the group consisting of organic hydroxy compounds and organic nitrogen compounds having a basic reaction as a tempering agent, contacting the resultant liquid mixture with a hydrocarbon mixture containing a low-boiling oleiin and saturated hydrocarbons to absorb said low-boiling oleiin, introducing resulting liquid olefin-containing hydroiiuoric acid containing said tempering agent into an alkylation zonealong with a low-boiling alkylatable hydrocarbon, maintaining the contents of said alkylation zone under alkylation A conditions, and recovering from eiiiuents of 'said alkylation zone a hydrocarbon fraction containing a higher-boiling hydrocarbon produced by said alkylation.

9. An improved process for alkylating hydrocarbons, which comprises reacting under alkylation conditions a lowLboiling alkylatable hydro.

carbon with an oleiin in the presence of liquid concentrated hydrouoric acid associated with between about 0.1 and 10 per cent by weight oi' a primary monohydric alcohol.

10. The process of claim 9 in which said alcohol is ethanol..

11. The process oi' claim 8 in which said tem-- pering agent is a primary monoalcohol.

12. The processv of claim 8 in which said tempering agent is methyl alcohol.

13. .The process of claim 8 in which said tempering agent is ethanol.

FREDERICK E. FREY. 

